EP3732141B1 - Wärmedämmendes glas, verfahren zu seiner herstellung und thermisches isolierglasprodukt - Google Patents

Wärmedämmendes glas, verfahren zu seiner herstellung und thermisches isolierglasprodukt Download PDF

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Publication number
EP3732141B1
EP3732141B1 EP18895939.9A EP18895939A EP3732141B1 EP 3732141 B1 EP3732141 B1 EP 3732141B1 EP 18895939 A EP18895939 A EP 18895939A EP 3732141 B1 EP3732141 B1 EP 3732141B1
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Prior art keywords
thermal insulating
layer
glass
insulating glass
protective
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EP18895939.9A
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French (fr)
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EP3732141A4 (de
EP3732141A1 (de
Inventor
Ce Shi
Chong ZHOU
Yunxin GU
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/478—Silica

Definitions

  • the present disclosure relates to a thermal insulating glass, a method for preparing the thermal insulating glass and a thermal insulating glass product.
  • Cs x WO 3 cesium tungsten bronze
  • the thermal insulating glass based on the cesium tungsten bronze material has been commercially available.
  • the existing thermal insulating glass can not be used in a hot bending process.
  • the main problem is that the existing thermal insulating glass can hardly withstand high temperature and strong oxidation environment during the hot bending process.
  • the existing thermal insulating glass may become obscure due to the migration of sodium-ions from the base glass.
  • the existing thermal insulating glass has poor wear resistance (for example, can not withstand the friction in the washing process).
  • the patent application published as No. CN103864313A discloses a thermal insulating glass having an infrared reflective multilayer structure.
  • the thermal insulating glass includes a transparent substrate, a barrier layer and a thermal insulating layer.
  • the barrier layer is positioned on the transparent substrate and includes tungsten oxide-containing silicon dioxide, titanium dioxide and aluminium oxide or a combination thereof.
  • the thermal insulating layer is positioned on the barrier layer and composed of a composite tungsten oxide.
  • This patent application also discloses a method for manufacturing the thermal insulating glass having an infrared reflective multilayer structure.
  • cesium tungsten bronze precursor and reducing gas such as N 2 , Ar, and H 2
  • cesium tungsten bronze precursor and reducing gas are typically used.
  • cesium tungsten bronze precursor and reducing gas are typically used.
  • a thermal insulating glass comprises: a glass substrate, a thermal insulating layer and a protective powder layer positioned on the thermal insulating layer.
  • the thermal insulating layer comprises composite tungsten oxide and a binder.
  • the composite tungsten oxide is represented by formula (1): M x WO 3-y A y (1), where M is an alkali metal element or an alkaline earth metal element, W is tungsten, O is oxygen, A is a halogen element, and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.5.
  • the binder comprises one or more of the following components: silicon dioxide, titanium dioxide, and aluminium oxide.
  • the protective powder layer comprises one or more of the following components: carbon powder, iron powder, zinc powder, aluminum powder, and reducing salt; and preferably, the thickness of the protective powder layer is from 0.01 mm to 5 mm, preferably from 0.1 mm to 1 mm, and more preferably 0.5 mm.
  • M cesium
  • the thickness of the thermal insulating layer is from 50 nm to 50 ⁇ m, preferably from 500 nm to 5 ⁇ m, and more preferably 1 ⁇ m.
  • the weight ratio of the binder to the composite tungsten oxide in the thermal insulating layer is from 1:1 to 1:1000, preferably from 1:10 to 1:200, and more preferably 1:100.
  • the thermal insulating glass further comprises a barrier layer positioned between the glass substrate and the thermal insulating layer.
  • the barrier layer comprises one or more of the following components: silicon dioxide, titanium dioxide, and aluminium oxide.
  • the purity of monocomponent silicon dioxide, titanium dioxide, and aluminium oxide is equal to or greater than 99%.
  • the dense degree of the barrier layer is equal to or greater than 90%.
  • the thickness of the barrier layer is from 5 nm to 500 nm, preferably from 10 nm to 200 nm, and more preferably 100 nm.
  • the thermal insulating glass also comprises a protective glass positioned on the protective powder layer.
  • a method for preparing the thermal insulating glass comprises the following steps:
  • thermo insulating glass product comprising the above thermal insulating glass is provided.
  • the positive effect of the present disclosure is that the thermal insulating glass according to the present disclosure can effectively block sodium-ions from the glass substrate, such that damage to lattice structure due to sodium-ion migration effect can be effectively avoided and the occurrence of obscuration can be prevented.
  • the thermal insulating glass has infrared reflectivity, high strength and good wear resistance, and can effectively resist the friction in the washing process.
  • the thermal insulating glass of the present disclosure can be applied in a hot bending or tempering process and can effectively resist high temperature and strong oxidation environment in the hot bending or tempering process.
  • compositions, process, method, article, or apparatus that includes a list of elements is not necessarily limited to include only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • one or more or “at least one” as used herein means one, two, three, four, five, six, seven, eight or more.
  • Glass in the term “glass substrate” as used herein is an amorphous inorganic non-metallic material, typically made from various inorganic minerals (e.g., quartz sand, borax, boric acid, barite, barium carbonate, limestone, feldspar, sodium carbonate, etc.) as the main raw materials and a small amount of auxiliary raw materials, and its main components are silicon dioxide and other oxides.
  • the "glass” here may be ordinary glass whose chemical composition is Na 2 SiO 3 , CaSiC 3 , SiO 2 or Na 2 O ⁇ CaO ⁇ 6SiO 2 , etc., and whose main component is silicate double salt (an amorphous solid with an irregular structure).
  • the "glass” here may also be colored glass into which certain metal oxides or salts are mixed to exhibit colors, or tempered glass obtained by a physical or chemical method.
  • reducing salt refers to salt having reducibility, and an example thereof is sulfite.
  • protective powder layer refers to a layer formed from powders having a protective effect.
  • protection glass refers to glass having a protective effect.
  • the meaning of “glass” in “protective glass” is consistent with the meaning of "glass” in “glass substrate”.
  • the present disclosure relates to a thermal insulating glass including a glass substrate and a thermal insulating layer.
  • the thermal insulating layer in the thermal insulating glass of the present disclosure includes composite tungsten oxide and a binder.
  • the composite tungsten oxide is represented by formula (1): M x WO 3-y A y (1), where M is an alkali metal element or an alkaline earth metal element, W is tungsten, O is oxygen, A is a halogen element, and 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 0.5.
  • M is an alkali metal element or an alkaline earth metal element, and examples thereof are lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) or any combination thereof.
  • A is a halogen element, and examples thereof are fluorine (F), chlorine (Cl), bromine (Br), iodine (I) or any combination thereof.
  • the composite tungsten oxide is represented by formula (2), M x WO 3 (2), where M, x, W and O are as defined above.
  • the composite tungsten oxide used in the present disclosure is commercially available, for example, from Sumitomo Metal Industries, Ltd.
  • the binder includes one or more of the following components: silicon dioxide, titanium dioxide, and aluminium oxide.
  • the thickness of the thermal insulating layer is from 50 nm to 50 ⁇ m, preferably from 500 nm to 5 ⁇ m, and more preferably 1 ⁇ m.
  • the weight ratio of the binder to the composite tungsten oxide in the thermal insulating layer is from 1:1 to 1:1000, preferably from 1:10 to 1:200, and more preferably 1:100.
  • the composite tungsten oxide material is a thermal insulating material having infrared reflectivity, so that infrared rays can be effectively reflected by the thermal insulating layer.
  • the binder can bond the composite tungsten oxide together, thereby effectively increasing the wear resistance of the thermal insulating layer.
  • the thermal insulating glass of the present disclosure further includes a barrier layer positioned between the glass substrate and the thermal insulating layer.
  • the barrier layer includes one or more of the following components: silicon dioxide, titanium dioxide, and aluminium oxide.
  • the purity of monocomponent silicon dioxide, titanium dioxide, and aluminium oxide is equal to or greater than 99%.
  • the dense degree of the barrier layer is equal to or greater than 90%.
  • the thickness of the barrier layer is from 5 nm to 500 nm, preferably from 10 nm to 200 nm, and more preferably 100 nm.
  • Sodium-ions from the glass substrate can be effectively blocked by the barrier layer, such that damage to lattice structure due to sodium-ion migration effect can be effectively avoided and the glass can be prevented from being obscured.
  • the thermal insulating glass of the present disclosure further includes a protective powder layer positioned on the thermal insulating layer.
  • the protective powder layer includes one or more of the following components: carbon powder, iron powder, zinc powder, aluminum powder, and reducing salt.
  • the reducing salt include, but are not limited to, sulfite.
  • the thickness of the protective powder layer is from 0.01 mm to 5 mm, preferably from 0.1 mm to 1 mm, and more preferably 0.5 mm.
  • the reducing materials do not react with the materials of the thermal insulating layer and can provide protective effect.
  • the protective powder layer can effectively prevent the surface of the thermal insulating glass from being oxidized.
  • the thermal insulating glass of the present disclosure further includes a protective glass positioned on the protective powder layer.
  • the protective glass can also effectively prevent the surface of the thermal insulating glass from being oxidized and provide better protection for the thermal insulating glass.
  • the present disclosure also relates to a method for preparing the thermal insulating glass of the present disclosure.
  • the method includes the following steps:
  • the glass substrate is used as a basis for the thermal insulating glass.
  • the preparation method of the present disclosure further includes a step (a1) of providing a barrier layer on the glass substrate.
  • a solution for the barrier layer is coated on the surface of the glass substrate and dried to form the barrier layer.
  • the coating process is preferably performed by a roll coating method.
  • the solution for the barrier layer includes one or more of the following components: silicon dioxide, titanium dioxide, and aluminium oxide.
  • the purity of monocomponent silicon dioxide, titanium dioxide, and aluminium oxide is equal to or greater than 99%.
  • the dense degree of the formed barrier layer is equal to or greater than 90%.
  • the solution for the barrier layer is a solution of the corresponding component.
  • silicon dioxide a silicon dioxide solution may be adopted.
  • the silicon dioxide solution is obtained by the following preparation method: tetraethyl orthosilicate is mixed with hydrochloric acid and they are stirred; the weight ratio of tetraethyl orthosilicate to hydrochloric acid is from 5:1 to 1:50; and the stirring temperature is from 15 to 25°C and the stirring time is from 4 to 10 hours.
  • the drying temperature is from 80 to 200°C and the drying time is from 3 s to 60 s.
  • the speed of the conveyor belt is from 5 to 15 m/min and the speed of the rubber roller is from 5 to 15 m/min.
  • the thermal insulating layer is provided on the glass substrate. That is, a mixed solution of a composite tungsten oxide solution and a binder solution is coated on the surface of the glass substrate and dried to form the thermal insulating layer.
  • the coating process is preferably performed by a roll coating method.
  • the step (b) is as follows: a mixed solution of a composite tungsten oxide solution and a binder solution is coated on the surface of the barrier layer and dried to form the thermal insulating layer.
  • the binder solution is a solution of the corresponding component.
  • a silicon dioxide solution may be adopted.
  • the silicon dioxide solution is mixed with the composite tungsten oxide solution.
  • the solid content of the composite tungsten oxide solution is from 5 to 50 %.
  • the weight ratio of silicon dioxide to composite tungsten oxide is from 1:1 to 1:1000, preferably from 1:10 to 1:200, and more preferably 1:100.
  • the drying temperature is from 80 to 200°C, and the drying time is from 3 s to 60 s.
  • the speed of the conveyor belt is from 5 to 15 m/min and the speed of the rubber roller is from 5 to 15 m/min.
  • the method of the present disclosure optionally includes a step (c) of providing a protective powder layer on the thermal insulating layer.
  • protective powder may be sprinkled by hand, or be dispersed in a solvent (such as water and ethanol) and sprayed on the surface of the thermal insulating layer.
  • a solvent such as water and ethanol
  • the method of the present disclosure optionally includes a step (d) of providing a protective glass on the protective powder layer.
  • the coating process described above can be performed by methods other than the roll coating method.
  • the method of spin coating, casting, bar coating, blade coating, wire bar coating, or dip coating may be employed.
  • the barrier layer is described as being positioned on the glass substrate in the above implementations, the description only indicates the positional relationship between the barrier layer and the glass substrate.
  • the barrier layer may be disposed in contact with the surface of the glass substrate.
  • Other layers may also be provided between the barrier layer and the glass substrate.
  • the thermal insulating layer is described as being positioned on the barrier layer, other layers may also be provided between the thermal insulating layer and the barrier layer.
  • the thermal insulating glass of the present disclosure can effectively block sodium-ions from the glass substrate, such that damage to lattice structure due to sodium-ion migration effect can be effectively avoided and the glass can be prevented from being obscured. Moreover, the thermal insulating glass has infrared reflectivity, high strength and good wear resistance, and can effectively resist the friction in the washing process. Moreover, the thermal insulating glass of the present disclosure can be applied in a hot bending or tempering process and can effectively resist high temperature and strong oxidation environment in the hot bending or tempering process.
  • Tetraethyl orthosilicate is mixed with hydrochloric acid (HCl) with a pH of 2 to prepare a silicon dioxide solution.
  • TEOS and hydrochloric acid are each 2 kg, and they are stirred at room temperature (25°C) for 4 hours.
  • the silicon dioxide solution is applied on the glass substrate by roll coating.
  • the purity of the silicon dioxide is 99%.
  • the speed of the conveyor belt is 10 m/min and the speed of the rubber roller is 12 m/min.
  • After the silicon dioxide solution has been applied on the glass substrate they are dried at a temperature of 100°C for 10 s to form a barrier layer.
  • the dense degree of the barrier layer is 90%.
  • the thickness of the barrier layer is 100 nm.
  • the silicon dioxide solution is mixed with a cesium tungsten bronze solution.
  • the solid content of the cesium tungsten bronze solution is 20%.
  • the weight ratio of silicon dioxide to cesium tungsten bronze in the mixed solution is 1:100.
  • the mixed solution is applied on the barrier layer positioned on the glass substrate by roll coating.
  • the speed of the conveyor belt is 14 m/min and the speed of the rubber roller is 14 m/min.
  • After the mixed solution has been applied on the barrier layer they are dried at a temperature of 100°C for 20 s to form a thermal insulating layer.
  • the thickness of the thermal insulating layer is 1 ⁇ m.
  • a thermal insulating glass of Embodiment 1 is obtained by the above method, and the thermal insulating glass includes a glass substrate 10, a barrier layer 11 positioned on the glass substrate 10 and a thermal insulating layer 12 positioned on the barrier layer 11 (see Fig. 1 ).
  • a protective powder layer is provided on the thermal insulating layer of the thermal insulating glass, and the protective powder layer includes carbon powder.
  • the protective powder is dispersed in water and sprayed on the surface of the thermal insulating layer.
  • the thickness of the protective powder layer is 0.5 mm.
  • a protective glass is provided on the protective powder layer, and the protective glass may be a commercially available ordinary glass having a thickness of 2.1 mm.
  • a thermal insulating glass of Embodiment 3 is obtained by the above method.
  • the thermal insulating glass of Embodiment 3 further includes a protective powder layer 13 positioned on the thermal insulating layer 12 and a protective glass 14 positioned on the protective powder layer 13 (See Fig. 2 ).
  • TEOS tetraethyl orthosilicate
  • IPA isopropanol
  • HCl hydrochloric acid
  • the prepared hydrochloric acid solution is slowly added to the tetraethyl orthosilicate solution, and they are stirred for 4 hours and coated on a substrate by wet coating to obtain a sample.
  • the sample is sintered at 550°C for 60 minutes.
  • High temperature oxidation resistance test samples 1-3 and the comparative sample 1 (respectively corresponding to Embodiments 1-3 and Comparative Embodiment 1) are treated in turn by a glass hot bending process (650°C, 15 min), and transmission spectrums (TEs) before and after the treatment are measured.
  • TEs transmission spectrums
  • a lower TE in the infrared region indicates a better thermal insulation effect after treated by the hot bending process.
  • the TE curves of the four samples after treated by the hot bending process are shown in Fig. 3 .
  • the TEs of the samples 1-3 are lower than that of the comparison sample 1, indicating that the samples 1-3 have a better thermal insulation effect than the comparative sample 1 after treated by the hot bending treatment.
  • the thermal insulation effect of the sample 2 is better than that of the sample 1
  • the thermal insulation effect of the sample 3 is better than that of the sample 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
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  • Composite Materials (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass (AREA)

Claims (9)

  1. Wärmeisolierendes Glas, umfassend:
    ein Glassubstrat;
    eine wärmeisolierende Schicht; und
    eine schützende Pulverschicht, die auf der wärmeisolierenden Schicht positioniert ist,
    wobei die wärmeisolierende Schicht Verbundwolframoxid und ein Bindemittel umfasst,
    und wobei das Verbundwolframoxid durch die Formel (1) dargestellt wird:

            MxWO3-yAy     (1),

    und wobei M ein Alkalimetallelement oder ein Erdalkalimetallelement ist, W Wolfram ist, O Sauerstoff ist, A ein Halogenelement ist und 0 < x ≤ 1 und 0 ≤ y ≤ 0,5,
    und wobei das Bindemittel eine oder mehrere der folgenden Komponenten umfasst: Siliziumdioxid, Titandioxid und Aluminiumoxid,
    und wobei die schützende Pulverschicht eine oder mehrere der folgenden Komponenten umfasst: Kohlenstoffpulver, Eisenpulver, Zinkpulver, Aluminiumpulver und reduzierendes Salz;
    und wobei vorzugsweise die Dicke der schützenden Pulverschicht von 0,01 mm bis 5 mm, vorzugsweise von 0,1 mm bis 1 mm und mehr bevorzugt 0,5 mm, beträgt.
  2. Wärmeisolierendes Glas nach Anspruch 1, wobei y = 0 ist.
  3. Wärmeisolierendes Glas nach Anspruch 1 oder 2, wobei M Cäsium ist.
  4. Wärmeisolierendes Glas nach einem der Ansprüche 1 bis 3, wobei die Dicke der wärmeisolierenden Schicht von 50 nm bis 50 µm, vorzugsweise von 500 nm bis 5 µm und mehr bevorzugt 1 µm, beträgt.
  5. Wärmeisolierendes Glas nach einem der Ansprüche 1 bis 4, wobei das Gewichtsverhältnis des Bindemittels zu dem Verbundwolframoxid in der wärmeisolierenden Schicht von 1 : 1 bis 1 : 1000, vorzugsweise von 1 : 10 bis 1 : 200 und mehr bevorzugt 1 : 100, beträgt.
  6. Wärmeisolierendes Glas nach einem der Ansprüche 1 bis 5, wobei das wärmeisolierende Glas ferner eine Sperrschicht umfasst, die zwischen dem Glassubstrat und der wärmeisolierenden Schicht angeordnet ist;
    wobei vorzugsweise die Sperrschicht eine oder mehrere der folgenden Komponenten umfasst: Siliziumdioxid, Titandioxid und Aluminiumoxid;
    wobei vorzugsweise die Reinheit der Monokomponente Siliziumdioxid, Titandioxid und Aluminiumoxid gleich oder größer als 99 % ist;
    wobei vorzugsweise der dichte Grad der Sperrschicht gleich oder größer als 90 % ist;
    und wobei vorzugsweise die Dicke der Sperrschicht von 5 nm bis 500 nm, vorzugsweise von 10 nm bis 200 nm und mehr bevorzugt 100 nm, beträgt.
  7. Wärmeisolierendes Glas nach einem der Ansprüche 1 bis 6, wobei das wärmeisolierende Glas ferner ein schützendes Glas, das auf der schützenden Pulverschicht positioniert ist, umfasst.
  8. Verfahren zum Herstellen des wärmeisolierenden Glases nach einem der Ansprüche 1 bis 7, umfassend die folgenden Schritte:
    (a) Bereitstellen eines Glassubstrats;
    (a1) optional, Bereitstellen einer Sperrschicht auf dem Glassubstrat;
    (b) Bereitstellen einer wärmeisolierenden Schicht auf dem Glassubstrat oder auf der Sperrschicht;
    (c) Bereitstellen einer schützenden Pulverschicht auf der wärmeisolierenden Schicht;
    (d) optional, Bereitstellen eines schützenden Glases auf der schützenden Pulverschicht.
  9. Wärmeisolierendes Glaserzeugnis, umfassend das wärmeisolierende Glas nach einem der Ansprüche 1 bis 7.
EP18895939.9A 2017-12-29 2018-12-25 Wärmedämmendes glas, verfahren zu seiner herstellung und thermisches isolierglasprodukt Active EP3732141B1 (de)

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138096A (zh) * 2018-11-05 2020-05-12 法国圣戈班玻璃公司 一种夹胶玻璃及其制备方法
CN111498906B (zh) * 2019-07-17 2022-05-10 中国科学院上海硅酸盐研究所 透明遮热材料、透明遮热微粒子分散体及其制法及用途
CN110423018A (zh) * 2019-09-12 2019-11-08 重庆友友利鸿玻璃有限公司 一种隔热玻璃制备方法
CN113840727A (zh) * 2020-04-15 2021-12-24 法国圣戈班玻璃厂 具有防晒涂层的交通工具装配玻璃
CN113121111A (zh) * 2021-03-18 2021-07-16 上海大学 隔热节能玻璃及其制备方法
CN116553836B (zh) * 2023-07-08 2023-09-22 内蒙古科技大学 一种钨青铜掺杂隔热玻璃及其制备方法

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3468871B2 (ja) 1994-10-14 2003-11-17 橋本フォーミング工業株式会社 樹脂成形品およびその製造方法
GB9619134D0 (en) 1996-09-13 1996-10-23 Pilkington Plc Improvements in or related to coated glass
US20150153478A1 (en) * 2007-04-18 2015-06-04 Sumitomo Metal Mining Co., Ltd. Electroconductive particle, visible light transmitting particle-dispersed electrical conductor and manufacturing method thereof, transparent electroconductive thin film and manufacturing method thereof, transparent electroconductive article that uses the same, and infrared-shielding article
JP2008273501A (ja) 2007-04-06 2008-11-13 Nippon Sheet Glass Co Ltd モール付きガラス及びその製造方法
FR2916380B1 (fr) 2007-05-21 2009-07-31 Saint Gobain Procede et dispositif de surmoulage d'un element vitre par une portion de joint comportant un insert, vitrage et insert notamment pour ce procede.
EP2360220B1 (de) * 2008-11-13 2015-03-18 Sumitomo Metal Mining Co., Ltd. Infrarotsperrpartikel, herstellungsverfahren dafür, davon gebrauch machende infrarotsperrpartikeldispersion sowie infrarotsperrbasis
EP2230118B1 (de) 2009-03-17 2012-05-30 Pilkington Italia S.p.A. Fahrzeugverglasung mit darauf montierter Zierleiste
TWI402218B (zh) * 2009-12-16 2013-07-21 Ind Tech Res Inst 透明隔熱材料、其製造方法以及透明隔熱結構
CN102145980B (zh) * 2010-02-08 2013-05-01 财团法人工业技术研究院 透明隔热材料、其制造方法以及透明隔热膜
JP5781735B2 (ja) * 2010-03-02 2015-09-24 株式会社ブリヂストン 熱線遮蔽複層ガラス
FR2961440B1 (fr) 2010-06-16 2014-10-10 Saint Gobain Vitrage comprenant un insert a element de pression, procede de fabrication du vitrage et insert pour le vitrage.
TWI408183B (zh) * 2010-12-07 2013-09-11 Ind Tech Res Inst 隔熱材料及其製造方法
DE102012014689A1 (de) 2012-05-10 2013-11-14 Parat Beteiligungs Gmbh Kraftfahrzeugverdeck
EP2874193B1 (de) * 2012-07-13 2019-11-06 LG Chem, Ltd. Folie zur fotothermischen umwandlung mit guter lichtdurchlässigkeit von sichtbarem licht und übertragungsfolie für oled damit
TWI458629B (zh) * 2012-12-17 2014-11-01 Ind Tech Res Inst 紅外線反射性多層結構及其製法
TWI531602B (zh) * 2012-12-28 2016-05-01 財團法人工業技術研究院 透明隔熱組成物
US9434652B2 (en) * 2013-07-23 2016-09-06 Industrial Technology Research Institute Infrared absorption material, method for fabricating the same, and thermal isolation structure employing the same
EP2905128A1 (de) * 2014-02-05 2015-08-12 Kuraray Europe GmbH Verbundglaslaminate mit Wärmestrahlung abschirmenden Eigenschaften auf Basis von dünnen Folien aus weichmacherfreiem Polyvinylacetal
TWI640479B (zh) * 2014-02-07 2018-11-11 加美嘉華光電材料股份有限公司 複合氧化鎢奈米粒子之製造方法
CN114771051A (zh) 2014-02-25 2022-07-22 积水化学工业株式会社 夹层玻璃用中间膜、夹层玻璃用中间膜的制造方法及夹层玻璃
US9114765B1 (en) 2014-05-30 2015-08-25 Ford Global Technologies, Llc Direct load side door pillar applique with integrated channel
US9079480B1 (en) 2014-06-06 2015-07-14 Toyota Motor Engineering & Manufacturing North America, Inc. Glass run weather strip assembly
TWI523919B (zh) * 2014-12-04 2016-03-01 財團法人工業技術研究院 具有防霧與隔熱功能之塗料組成物、其製法及薄膜
JP2018015898A (ja) * 2014-12-05 2018-02-01 コニカミノルタ株式会社 遮熱フィルム
CN105984190A (zh) * 2015-02-13 2016-10-05 林宽 隔热膜及隔热材料
JP2018054641A (ja) * 2015-02-20 2018-04-05 コニカミノルタ株式会社 遮熱フィルム
EP3095601B1 (de) * 2015-05-22 2023-07-05 Kuraray Europe GmbH Penetrationsresistentes, mit zwischenschichtfilmschichten mit reduzierter haftung und niedrigem weichmachergehalt hergestelltes verbundglas
CN106987205B (zh) * 2016-01-20 2019-05-21 富创国际顾问有限公司 具隔热抗污的涂料组成物、其制备方法及具有隔热抗污涂料组成物的薄膜与透光板
WO2018083280A1 (en) * 2016-11-07 2018-05-11 Kuraray Europe Gmbh Fabrication process for laminated glass comprising a functional film
JP6614110B2 (ja) 2016-11-24 2019-12-04 トヨタ自動車株式会社 車両用窓ガラスのモール構造
CN107189501B (zh) 2017-06-08 2019-08-20 东莞大熙节能科技有限公司 可钢化的隔热涂料及其制备方法及其制得的隔热钢化玻璃
CN207128588U (zh) 2017-08-30 2018-03-23 长城汽车股份有限公司 车门门缝密封条、车门及汽车

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EP3732141A4 (de) 2021-09-22
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US20200354265A1 (en) 2020-11-12
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